Resorcinal-derived copolycarbonate compositions

ABSTRACT

A composition comprising a block aromatic copolycarbonate having from about 2 to 30 mole % of the total repeating carbonate units derived from resorcinol.

This is a divisional of application Ser. No. 07/863,918 filed on Apr. 6,1992, now U.S. Pat. No. 5,336,751.

BACKGROUND OF THE INVENTION

Aromatic polycarbonates are well known for their excellent properties.However it has always been a goal of workers in the area to preparepolycarbonates which retain as many of the excellent properties ofaromatic polycarbonates to as great extent as possible, particularly theproperties of bisphenol-A polycarbonate, while improving the melt flowof the polymer. A significant amount of the work in this area hasfocused on the introduction of certain comonomers into the structure tobring about such desired effects. For example copolyestercarbonateshaving aliphatic ester groupings have significantly improved flow butalso display decreased thermal properties compared to the polycarbonate.

A novel copolycarbonate has been discovered which has substantiallyincreased flow together with high thermal stability. This is achievedwithout introducing aliphatic repeating units into the polymer. Thecomposition is a block copolymer and is prepared by standard interfacialtechniques.

SUMMARY OF THE INVENTION

In accordance with the invention there is a composition comprising ablock copolycarbonate having from about 2 to 30 mole % of the totalrepeating carbonate units derived from resorcinol.

Another aspect of the invention is preparing the inventive compositionunder interfacial reaction conditions.

Color improvement of the final composition is obtained by purging withan inert gas such as nitrogen each of the reaction formulation chemicalsfor an appropriate time, either alone or together as the formulationmixture prior to reaction with the carbonate precursor and/ormaintaining a neutral pH, about 6 to 8 until the beginning of thecarbonation reaction.

DETAILED DESCRIPTION OF THE INVENTION

Resorcinol has been mentioned as a possible monomer or comonomer foraromatic polycarbonates for many years. However the only aromaticpolycarbonate which has been made to date having resorcinol thereinappears to be a 50--50 mole % copolycarbonate of resorcinol andbisphenol-A reported at page 68 of Schnell, Chemistry and Physics ofPolycarbonates, Interscience Publishers, 1964. However, no propertiesare reported except for its melting range and Tg. The blockcopolycarbonates of this invention have excellent melt flow togetherwith the retention to a great extent of other important properties ofpolycarbonates, as well as high thermal stability. In polymerterminology a random copolymer structure is dependent upon the molefraction of the various comonomers. A block copolymer has a greaternumber of a single monomer grouped together in a block.

The dihydric phenols other than resorcinol which can be used in theblock copolycarbonate of this invention may be represented by thegeneral formula. ##STR1## wherein:

R is independently selected from halogen, monovalent hydrocarbon, andmonovalent hydrocarbonoxy radicals;

R¹ is independently selected from halogen, monovalent hydrocarbon, andmonovalent hydrocarbonoxy radicals;

W is selected from divalent hydrocarbon radicals, ##STR2##

n and n¹ are independently selected from integers having a value of from0 to 4 inclusive; and

b is either zero or one.

The monovalent hydrocarbon radicals represented by R and R¹ include thealkyl, cycloalkyl, aryl, aralkyl and alkaryl radicals. The preferredalkyl radicals are those containing from 1 to about 12 carbon atoms. Thepreferred cycloalkyl radicals are those containing from 4 to about 8ring carbon atoms. The preferred aryl radicals are those containing from6 to 12 ring carbon atoms, i. e., phenyl, naphthyl, and biphenyl. Thepreferred alkaryl and aralkyl radicals are those containing from 7 toabout 14 carbon atoms.

The preferred halogen radicals represented by R and R¹ are chlorine andbromine.

The divalent hydrocarbon radicals represented by W include the alkylene,alkylfdene, cycloalkylene and cycloalkylidene radicals. The preferredalkylene radicals are those containing from 2 to about 30 carbon atoms.The preferred alkylidene radicals are those containing from 1 to about30 carbon atoms. The preferred cycloalkylene and cycloalkylideneradicals are those containing from 6 to about 16 ring carbon atoms.

The monovalent hydrocarbonoxy radicals represented by R and R¹ may berepresented by the formula - OR² wherein R² is a monovalent hydrocarbonradical of the type described hereinafore. Preferred monovalenthydrocarbonoxy radicals are the alkoxy and aryloxy radicals.

Some illustrative non-limiting examples of the dihydric phenols fallingwithin the scope of Formula II include:

2,2-bis(4-hydroxyphenyl)propane (bisphenol-A);

2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane;

2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane;

1,1-bis(4-hydroxyphenyl)cyclohexane;

1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane;

1,1-bis(4-hydroxyphenyl)decane;

1,4-bis(4-hydroxyphenyl)propane;

1,1-bis(4-hydroxyphenyl)cyclododecane;

1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane;

4,4-dihydroxydiphenyl ether;

4,4-thiodiphenol;

4,4-dihydroxy-3,3-dichlorodiphenyl ether; and

4,4-dihydroxy-2,5-dihydroxydiphenyl ether.

Other useful dihydric phenols which are also suitable for use in thepreparation of the above polycarbonates are disclosed in U.S. Pat. Nos.2,999,835; 3,028,365; 3,334,154; and 4,131,575, all of which areincorporated herein by reference.

The carbonate precursor utilized in the invention can be any of thestandard carbonate precursors such as phosgene, and the like. Whileusing an interfacial process it is also preferred to use a standardcatalyst system well known in the synthesis of polycarbonates. A typicalcatalyst system is that of an amine system such as tertiaryamine,amidine or guanidine. Tertiary amines are generally employed in suchreactions. Trialkylamines such as triethylamine are generally preferred.

In order to control molecular weight, it is standard practice to utilizea chain stopping agent which is a monofunctional compound. This compoundwhen reacting with the appropriate monomer provides a non-reactive end.Therefore the quantity of chain stopping compound controls .themolecular weight of the polymer. Bulkier chain terminators than phenolshould provide substantially better retention of physical propertiessuch as impact. Examples of these bulkier substituents includeparatertiarybutylphenol, isononyl phenol, isooctyl phenol, cumyl phenolssuch as meta and paracumyl phenol, preferably paracumyl phenol, as wellas chromanyl compounds such as Chroman I.

The weight average molecular weight of the copolycarbonate can generallyvary from about 10,000 to about 100,000 as measured by GPC, using apolystyrene standard corrected for polycarbonate. A preferred weightaverage molecular weight is from about 14,000 to about 40,000.

The block copolymer is made under standard interfacial conditions. Theseconditions have been described in numerous publications including thepatents previously mentioned in this document which are hereinincorporated by reference. Essentially, an aqueous alkaline saltsolution of the dihydric phenol is contacted with an organic solvent inwhich the ensuing polycarbonate is soluble, such as methylene chloride,ethylene dichloride, chloroform, preferably methylene chloride, togetherwith a carbonate precursor, preferably phosgene, with mixing of the twophases. Also generally present are a catalyst system and a chainterminator. The polycarbonate is isolated from the organic phase.

It has been found that in preparing this particular composition thatcolor of the polymer can be improved by the purging of the formulationmixture and particularly the reactant resorcinol as well as BPA with aninert gas such as nitrogen, carbon dioxide, argon and the like,preferably nitrogen for an appropriate time period, at least about 1minute and generally from about 5 to 30 minutes. This can beconveniently done in the reaction vessel wherein all the reactants andsolvents are included immediately prior to the addition of the carbonateprecursor, preferably phosgene.

As a separate step in addition to or in lieu thereof for improvingcolor, the formulation mixture is maintained at an essentially neutralpH, about 6-8 until the beginning of the addition of the carbonateprecursor or the catalyst, whichever occurs first.

The polymers of this invention are block copolycarbonates. Thesepolymers have a resorcinol content of from about 2 to 30 mole percentbased on the total dihydric phenol present in the copolymer, preferablyabout 5 to 20 mole percent resorcinol. As well as having the advantagespreviously mentioned and demonstrated in the examples below, thepolymers should also have increased flame retardance compared tocopolyestercarbonates having aliphatic ester repeating units.

Below are the exemplified compositions of this invention. These examplesare intended to illustrate and are not included to narrow the genericnature of the invention.

EXPERIMENTAL PROCEDURE

Into a reactor was placed:

Methylene chloride=500 ml

H₂ O=400 ml

Phenol=0.3 mole % of dihydric phenol

BPA+resorcinol=0.25 moles

The formulation was purged with nitrogen for fifteen (15) minutes whilebeing maintained at a neutral pH (6 to 8). 2 mole % of triethylaminecatalyst was quickly added to the reactor while raising the pH to alevel of 9.5. Phosgene was then immediately blown into the reactor to aquantity of 0.325 moles over a time period of sixteen (16) minutes at asteady rate, the first half of the phosgene was added while maintainingthe pH at about 10, the second half while maintaining the pH at about10.5. Constant stirring of the reactor contents occurred during theentire reaction.

The brine and organic phase were then separated. The organic phase waswashed four (4) times with dilute HCl (2% ) and four (4 ) times withdeionized water. The polymer was precipitated using hot water under highshear.

Physical properties of the polymers are shown below with the followingabbreviations and test explanations.

RS is resorcinol.

Mw and Mn are determined by GPC against polystyrene standard with apolycarbonate correction.

Tg is measured by DSC.

Td5 is decomposition temperature at 5% weight loss and is measured bythermal gravimetric analysis.

MVI is melt viscosity index.

ΔMw 300° C. tail is a test utilized to show thermal stability and is thepercent change in Mw occurring due to the MVI test at 300° C.

    __________________________________________________________________________         Reaction                                                                           HPLC                                                                Example                                                                            RS   RS   Mw  Mn  Mw/                                                                              Tg Td5                                                                              MVIcc/10 min                                                                              ΔMw                         #    Mole %                                                                             Mole %                                                                             x,1000                                                                            x1,000                                                                            Mn °C.                                                                       °C.                                                                       250° C.                                                                    280° C.                                                                    300° C.                                                                    300° C.                    __________________________________________________________________________                                                Tail                              Control                                                                             0   0    27.6                                                                              10.5                                                                              2.61                                                                             150                                                                              440                                                                              2.2 6.5 15.0                                                                              -4.4                              1    10   8.0  26.0                                                                              9.3 2.80                                                                             144                                                                              427                                                                              2.9 9.9 21.2                                                                              -2.6                              2    20   17.1 24.6                                                                              8.0 3.06                                                                             137                                                                              427                                                                              4.2 17.8                                                                              39.9                                                                              -2.8                              __________________________________________________________________________

As is clearly demonstrated by the data the Tg is somewhat reduced by theaddition of resorcinol. However the processability of the polymer asmeasured by MVI is markedly increased even though resorcinol is anaromatic moiety. Finally and of great significance and unpredictable isthe fact that the thermal stability of the copolymer as measured by ΔMw300° C. tail, is increased over the BPA homopolycarbonate.

What is claimed is:
 1. An aromatic copolycarbonate comprising a reactionproduct of a dihydric phenol, resorcinol and a carbonate precursorwherein the amount of said resorcinol is sufficient to provide fromabout 2 to 30 mole % resorcinol derived carbonate units of the totalcarbonate units, and wherein said dihydric phenol and said resorcinolare a reaction formulation which is purged with an inert gas prior toreaction with the carbonate precursor.
 2. The aromatic copolycarbonateof claim 1, wherein the inert gas is nitrogen.
 3. The aromaticcopolycarbonate of claim 2, wherein the change in the weight averagemolecular weight of the aromatic copolycarbonate at 300° C. is less than4%.
 4. The aromatic copolycarbonate of claim 1, wherein the reactionformulation is maintained at a pH between about 6-8 prior to reactionwith the carbonate precursor.
 5. The aromatic copolycarbonate of claim1, wherein the dihydric phenol comprises2,2-bis(4-hydroxyphenyl)propane.
 6. An aromatic copolycarbonateconsisting essentially of a reaction product of a dihydric phenol,resorcinol and a carbonate precursor wherein the amount of saidresorcinol is sufficient to provide from about 2 to 30 mole % resorcinolderived carbonate units of the total carbonate units, and wherein saiddihydric phenol and said resorcinol are a reaction formulation which ispurged with an inert gas prior to reaction with the carbonate precursor.7. The composition in accordance with claim 1 wherein thecopolycarbonate is a bisphenol-A resorcinol copolycarbonate.
 8. Thecomposition in accordance with claim 1 wherein Resorcinol is from about5 to 20 mole %.